Paevt oil



Patented Nov. 1 1935 UNITED STATES PATENT OFFICE PAINT OIL Frank W. Corkery, Grafton, Pa. No Drawing. Application February 3, 1936, Se-

rial No. 62,045.

9 Claims.

This invention relates to the production of a paint oil of mixed composition, comprising a mineral component, together with a marine or' vegetable component.

In accordance with my invention, I have taken the material known as still residue, to be hereinafter defined, and, by appropriately treating it, together with a drying or semidrying oil of animal, vegetable or marine origin, have produced a paint oil of mixed composition in which the still residue is in a state of solution in the oil.

The term still residue includes residual liquid products resulting from the purification efiected upon various fractions and derivatives of an oily material obtained from the distillation of coking of coal, known as light oil. The term light oil defines those fractional distillation products of coal most of which boil below 218 C., and which contain a number of recoverable ingredients, among such being benzene, toluene, xylene, trimethyl benzene, ethyl benzene, coumarone, indene, cumene, cymene, hemmilithene, hydrindene, and in general methyl, ethyl, propyl and amyl addition or substitution products of the benzene ring group of aromatic chemicals.

In subjecting the light oil to a purifying acid wash, and in distilling the light oil, liquid residue, comprising lower polymers, reaction products, and monomers of relatively large molecular size, remains. This residual material is known as still residue.

The product known as still residue includes residuum from the initial or crude stills used in purifying light oil and the light oil cuts, and residuum from the final or pure stills used in purifying light oil and the light oil cuts. Regardless of its proximate derivation, the re- 40 siduum from the stills used in any stage of puri-- fying light oil, or a mixture of the product from stills of different type, is herein designated coalderived still residue, or merely still residue.

In accordance with my invention, I make a mixed or composite paint oil or stock comprising still residue which is to a desired extent oxidized. Desirably, if the still residue content of the mixture comprises a relatively large proportion of the whole, oxidation is performed simultaneously upon both the still residue and the drying oil in the physical presence of each other, in order to obtain increased compatibility between the oxidized still residue and the oxidized drying oil.

This invention is based upon my observation Renewed March 1, 1938 that all of the still residues have a substantial-iodine value, and that all may be substantially changed in their qualities by subjection to an oxidizing treatment which results in saturation of the material to an extent rendering it useful as an ingredient of paint stock. It is well-known that the drying oils, whether of vegetable or marine origin, have a relatively high iodine value. For example, the iodine value of soy bean oil is 130, the iodine value of linseed oil is 175 to 185, and the iodine value of fish oil, such as a mixture of menhaden oil and sardine oil, is approximately 175.

On blowing, the iodine value of soy bean oil is reduced'to 90, the iodine value of linseed oil is reduced to 100, and the iodine value of fish oil is reduced to 98, these oils being changed from thin liquids to heavy liquids. Most coal-derived still, residues have a high iodine value, and many havean iodine number of between and 150. I have found that, by blowing, oxidation of the still residue may be efiected to an extent indicated by a great reduction in iodine number, as, for example, a reduction of from to 65 or 70 in iodine number. If the still residue be blown by itself, it is changed from a heavy liquid to a pliable solid which has a melting-range of from F. to F.

The oxidation of coal-derived still residue imparts to the still residue a drying quality not previously possessed by it. This quality I have found to be imparted to the still residue in substantial degree even by an oxidation carried only to a point representing relatively slight oxida- 7 tion of the still residue, considered in terms of a numerical reduction in iodine value of the still residue. I have also found that an oxidation, which is relatively slight in terms of iodine value, increases the viscosity of the still residue to a substantial extent. By making a mixed or composite paint oil or stock of still'residue. which is, or has been subjected to oxidation, I am able to produce a paint oil of decreased cost, and which possesses valuable improvement in the elasticity of a film formed by it, and in other qualities which are attributable directly to the inclusion of the still residue in the stock.

By conducting an oxidizing treatment simultaneously upon an initial mixture of still residue and drying oil, I am able so to retain compatibility of the still residue and the drying oil that the mixed product is homogeneous under all normal conditions, and that the components of the mixture are soluble in each other in all proportions. Also, by subjecting'an initial mixture of 'still residue and drying oil to oxidation I am able,

by carrying oxidation of the mixture to a point which may be considered extreme; to produce a homogeneous solid, which is soluble in selected solvents, but which is relatively insoluble. in certain of the solvents commonly used as thinners.

I.shall describe a procedure which may be 7 1 considered typical for the production of a paint .after given, may be made in the conditions. of

oil, or stock, of relatively heavy body, it bein understood that such typical. procedure should be considered merelyas illustrating a mean, or intermediate, exemplification of a process involving the oxidation of a mixed batch of still residue and drying oil. It should be explained that many variations, some of which will be hereinthe process in order to obtain aproduct having qualities desirable for particular purposes.

In conducting this illustrative procedure, Ihave introduced a mixture of fish oil and liquid; still.

.residue comprising substantially equal volumes of these two componentsiinto a vessel provided withcoi'lsfor circulatingsteam', or other heating. 7 medium; and provided with'perforated coils'for 1 25; introducing'into the vessel under pressure a rela- 1 tively great volumeofhighly distributed Initially'bringing the temperature of the batch to' approximately 1'70'F. the air. was introduced in substantial volume. and dispersed in fine -streamsthrOugh the body of thepbatch. During a period of 5 days, the material was maintained substantially at its starting temperature, and the air was continuously blown ,through it. 'The temperature of approximately 170 F. was'found .adequate tomaintain the'batch in a condition' sufficiently liquid to permit the dispersal of air in' it, particularly to permit thoroughdispersion "of the air, if the .airpressure was slightly increased as the oxidizingreaction proceeded.

The resultant product was a heavy liquid, which exhibited a marked increase in viscosity. The initial viscosity'of the mixture having been noted as approximately '150 Saybolt, the treated;- mixture showed a viscosity of approximately 1800 saybolt. By test the mixture was found to 'have'befo're treatment an iodine value of 158 and after treatmentan iodine value of 91.

The' foregoing example .illustrates an ingre dient ratio of the paint oil composition which ob- ..tains the advantagesof a still residue inclusion,

the ingredients, while obtaining, products which are useful for particular purposes. For example, a variation in the ratio between the. drying oil. and the still residue, to include an I increased proportion. of drying, oil, increases the.

solubility of the resultant product in a manner to renderitsoluble in heavier. petroleum distillates of lower than average solvent power, in whichthe product of the examplegiven would not be adequately soluble 'Thms, a batch comprisingv 60% by volume of drying oil 13,1'1d.f10% by volume of still residue maybe treated under'the conditions given above to give a mixed paint oil havingsubstantially the viscosity of the mixed paintoilproducedby oxidation of equal volumes V of still residue and drying oil. While; as stated,

such productwould have-a somewhat increased 75, range oi -solubility in. petroleum distillates, it.

would possess in degree less adhesion than that" of a mixed paint oil comprising equal volumes of still residue and drying oil.

Particular utility is to be found in a mixed oxidized paint oil, in which the ratio of still residue to drying oil is increased above equality by volume. By increasing the proportional con tent of still residue in the composition, increased adhesion may be obtained. .In order that-the range. of solvents-usable withexamples; of the product containing a substantially increased ratio of still residue to paint oil may not be unduly limited, the conditions of the process are modified tolimit the extent of oxidation and the viscosity of the. mixed paint oil produced.

As an'exampleof my mixed paint oil, containing an .increased proportion of still residue, I

. have produceda paint oil', having high utility as a clear anti-rust coating for ferrous metals and thelike, by treating still residue and drying oil.

together in the ratioof volumes of still residue to 20'volumes of drying oil. This mixture, which.

may be consideredas comprising any of the drying oils as its initial oil content, was subjected to oxidizing treatment for. a period of approximately sixand one half days, during which the maximum temperature underwhich the mixture was blown was raised to about 195 F. The resultant product was a solid, elastic, transparent material having a melting-point of approximately F. This solid material may be cut' back by suitable solvent mixture, such as a solvent mixture comprising approximately 40% of aromatic hydrocarbon solvent, such as coal tar naphtha, and 60% of solvent petroleum. distillate, such as mineral spirits.

Because of its good adhesion and elasticity, the

ample and the'example first given as illustrating an intermediate or mean condition the still residue and the drying oil may be mixedin varying material when. deposited in a film forms an exproportionswithregard to the desirabilityof obr f taining the qualities of adhesion and elasticity in greater or lesser degree. and with regardto the desirability of rendering the product soluble in the less expensive solvents- "It-should be undeterminable within limits, aside from the relative proportions of-the two materials in the mix 'ture, by varying. the extent of oxidizing treat ment. That is, carrying the oxidation to the 7 higher stagesresults in somesacrifice of elasticity in the; resultant product... Even in such stages,

however, and even when comprising; arelatively. small proportion of the drying oil,.the product yet maybe considered .to be highly elastic.

I have observed thatthe solubility of the mixed oxidized material varies inversely with the quan'-' composition.

Til

residue than the other, the stage of oxidation'to;

which they; are carried being equal, the sample being. 'equal',*that one which is brought to the Also, the percentage in lower stage of oxidation will be soluble in the wider range of solvents.

Therefore, if it be desired to obtain the high adhesive quality, and other qualities attendant upon the inclusion of a high percentage of still residue in the composition, while retaining solubility in hydrocarbon solvents containing small percentages of aromatic hydrocarbons and in some highly specialized petroleum solvents, oxidation is to be terminated at a point which leaves the desired solubility of the composition, in conjunction with an adequate increase in the viscosity of the composition.

Taking, for example, the composition comp-rising 80% still residue and 20% drying oil, this I subject to oxidizing treatment for approximately six-and one half days, in order to obtain a filmforming material which is soluble in certain grades of the mixed hydrocarbon solvents. If this same percentage composition be subjected to oxidation for a five day period only, the resultant product has a melting-point of from 80 F. to F., and is soluble in those petroleum distillates having the greatest solvent power, and in mixed hydrocarbon solvents comprising a lower percentage content of aromatic hydrocarbon distillate.

Taking mixtures such as 85% raw still residue to 15% drying oil, and carrying the oxidizing process as far as possible, as, for example, to a point at which a temperature of 200 F. to 210 F. is necessary for the dispersion of the oxidizing air in the mixture undergoing treatment, I obtain a product which is soluble in the aromatic hydrocarbon solvents and in mixed hydrocarbon solvents containing a substantial quantity of aromatics. Such product has a melting-point of from F. to F. By similarly oxidizing a composition which is 90% still residue and 10% drying oil, I obtain a product which has a melting-point of approximately F. The completion of the oxidizing treatment is in this example evidenced by a final blowing temperature approximating 220 F. This product also is soluble in the aromatic hydrocarbon solvents and in the mixed hydrocarbon solvents containing a substantial quantity of aromatics.

Both these last named products may be utilized in making linoleum and like materials, and may be utilized as adhesives. The latter product is a gummy, rubber-like material possessing elasticity in a particularly marked degree.

In the general disclosure, above given, it should be understood that the higher temperatures given do not constitute critical factors, but that they relate to the maintenance of the composition undergoing treatment in a condition suitable for the dispersion of air therethrough. The necessity for a particular temperature in oxidizing the various percentage mixtures thus also indirectly indicates the stage to which oxidation has proceeded. The only critical temperature involved is the approximate temperature of F., which may be considered critical for the performance of substantial oxidation at a commercially practical rate.

It is to be emphasized that the process is one of simple oxidation, necessitating no preliminary or subsequent distillation or separation, or other treatment. It depends primarily on my appreciation of the fact that raw coal-derived still residue has" a substantial iodine value, and my discovery that this permits substantial change in the qualities of the still residue by oxidation. It depends also on my discovery that, as oxidized together, coal-derived 'still residue and the drying oils are soluble in each other in all proportions.

I also have discovered that when the raw drying oil and the raw still residue are oxidized together, the solubility of the resultant composition is far higher than would be anticipated by reference to the solubility of the still residue content if carried by itself to a corresponding stage of oxidation. This is particularly notable in those examples which contain a high content of still residue, and in which the mixture is carried to a high stage of oxidation. This phenomenon explains the relatively good solubility of the high meltingpoint examples given above, in which mixtures containing respectively 85% of still residue and 90% of still residue are carried to a high stage of oxidation.

The factors given above will enable any one to give some crude drying oils a slight oxidizing 7 treatment before blowing together the drying oil and the still residue, in order to prevent objectionable foaming. It may be observed also that it may be desirable to give the still residue a slight preliminary oxidation, followed by a moderate oxidizing treatment of a mixture of this still residue and the drying oil, when it is desired to produce a mixed paint oil of this composition which has a relatively low viscosity. Such preliminary oxidation of either component should, however, be strictly limited, in order that the mutual solubility of the components may not be seriously impaired.

As an example of operating variation, it is to be understood that it is possible, albeit with difficulty, to carry the oxidation of an equal mixture of liquid coal-derived still residue and oxidizable oil to a stage at which it has a meltingpoint in the neighborhood of 100 F. In line with this mentioned difiiculty, it may be noted that the oil has a tendency to gel under oxidation, which tendency is resisted proportionally by the presence of the still residue in admixture with the oil.

It should be understood that the complete content of the still residue may be, and desirably is, mixed with the drying oil. During blowing at the temperatures herein given, only a relatively small percentage of the lighter components of the still residue, such as naphthalene, naphtha, and light solvents are driven oil. The lower polymers and components of relatively heavy molecular composition are not driven off during blowing. The use of the entire still residue, rather than a topped still residue, contributes to elasticity of the product both in mass and in the form of a deposited film. The drying quality imparted to the still residue as a component of the composition is thus attributable directly to oxidation of the still residue, and is not due to topping nor to polymerization. For this reason, even the more lightly oxidized examples of the composition dry in a firm, non-tacky film, and the solid, high melting-point examples of the composition are non-tacky in mass.

In the appendant claims the term oxygen is used primarily to define the oxygen which is most simply used in its dilute occurrence as air.

', Ifroxygen i .ae ativ y pure fo m;. .h

concentrationthan inair, be used, th e progress oi oxidation in; the oxidizable mixture i is ac 'celerated. The progress of oxidation may also aromatics distilling below the boiling range of tarpas recovered in by-product coking. which 'residuum being; oily liquid stillQresidue from V 6,;the-distillation and purification of the 'lightoil 7 derived from theilight oil and which is capable compriseslower'polymers and heavy monomers otacquiring drying qualities andasphaltic char.- acteristics; by, oxidation, by oxygen dispersion through the mixture continued to a stage at which the mixture becomes solid at temperaturfi at least aselevated as normalroom temperature, while supplying to-the mixture heat sufiicient; to maintain; the mixture in a condition ggadequately liquid. for the oxygen dispersion, re-

sultantly toproduce a homogeneous elastic and transparent;film-forming mass in which the components-'are'mutually compatible as an incident'of their conditionof admixture during oxiuation. V

' 2. Theherein described method of producing a film-forming composition which comprises oxidizing, simultaneously in admixture oxidizable oil having drying qualities and residuum derived girom the'aromatic light oil which comprises the "aromatics distillingbelow the boiling range of tar' as recovered in by-product coking which residuum being an oily liquid still residue from the distillation'andpurification of the light oil comprises lower polymers and heavy monomers derived fromthe light oil and which is capable of acquiring by oxidation drying qualities and asphaltic characteristics by oxygen dispersion through the mixture continued to a stage at 'which the mixture acquires by oxidation substantial viscosity and relatively high drying qualities, whilesupplying to the mixture heat sufiicient to maintain the mixture in a condition adequately liquid forytheoxygen dispersion, re-

,sultantly to produce a homogeneous transparent film forming'bodyin' which the components are mutually compatible as an incident; of their condition of admixture during oxidation. 7 V

B JThe-herein described method of producing ;a film-forming composition which comprises oxidizing an oxidizable oil having drying qualities? and residuum; derived from the aromatic light oil-.whichcomprises the aromatics distilling below the boiling rangegof tar as recovered in by-product coking which residuurnbeingan oily liquid-still residu'e from the distillation and purification of the light oil comprises lower polymers and heavy monomers'derived'from the light oil and which is capable: of acquiring drying qualities wand asphaltic' characteristics by oxidation, the

oxidation-of theastill'residue being at least partially effected simultaneously with that of the' oxidiz'able oil by oxygen dispersion through a V mixture comprising the; oxidizable oil and the gstill; residue in which the; still residue initially is; at least below such stage of oxidation as would be,accelera ted by ozonizing air' used for oxidarender it incompatible with the oxidizable oil, such oxygen dispersion through the mixture being continuedto a stage at which the mixture acquires byoxidation substantial Viscosity and relatively high drying qualitiesyvhile supplying to the mixture heat sufficient to maintain the mixture in a conditionadequately liquid .for the oxygen dispersion, resultantly to produce a homo-. .geneous transparentfilm-forming body in which the components are mutually compatible as an incident of-their. condition of admixture during oxidation. I

4; The herein described method of producing a solid film-forming composition of relatively high melting-point, which comprises oxidizing an oxidizable'oil having drying qualities and residuum derived from the aromatic light oilwhich comprises the aromatics; distilling below the boiling range of tar as recovered in by-pmduot cok ing which residuum being an oily liquid 'still residue from the distillation and purification of i the light: oil comprises'lower polymers and heavy monomers derived from the light oil and which.

iscapable of acquiring drying qualities and'asphaltic characteristics by oxidation the oxidation of the still residue being at least partially effected simultaneously with that of the oxidizable. oil by oxygen dispersion through a mixture.

comprising the oxidizable' oil and the still residue in which the. still residue initially isat least belowsuch stage of oxidation as would renderit. incompatible with the oxidizable oil, such oxygen dispersion through the mixture being continued to a stage at which the mixture acquires byoxidation such melting-point that it is a solid at temperatures at least as high as normal room temperature while supplying to the mixture heatsufficient'to maintain the :mixture adequately liquid for the oxygen dispersion, resultantly to produce a homogeneous" elastic and transparent film-forming mass in -which the components are mutually compatible as an in cident of the condition of admixture during oxidation.

.5. The hereindescribed a solid film-forming composition of relatively high melting-pointwhich comprises oxidizing an method-of producing oxidizable oil having drying qualities ahd residuum derived from the aromatic light. oil which 'comprisesthe aromatics distilling below the 5011-.

ing range of tar as recovered in by-product cokingwhich residuum being an oily liquid still residue from the distillation and purification of the light oil comprises lower'polymers and heavy monomers derived from the light oil andwhich:

is capable of acquiring drying qualitiesand asphaltic characteristics bybxidation, the oxidation of thestill residue'being at least partially effected.simultaneously with that of the oxidizable oil by oxygen. dispersion through amixturei comprising the oxidizable oil and the still residue in which the latter preponderates andin which the still residue initially isat least below such stageof'oxidation as would render it incomp'atible with the oxidizable oil, such oxygen dis- 5 f persion through the mixture being continued to a stage at which the mixture acquires by oxida- 1 tion a melting-point substantially higher than normal, room temperature while supplying to the mixture heat-sufiicient to maintain the mixture adequately liquid for the oxygen dispersion, re-

sultan'tly'to produce a homogeneous elastic and transparent film-forming mass in which'the components are mutually compatible as an incident of their condition of admixture during oxidation.

6. The herein described method of producing a solid film-forming composition of relatively high melting-point which comprises simultaneously oxidizing a mixture of oxidizable oil having drying qualities and residuum derived from the aromatic light oil which comprises the aromatics distilling below the boiling range of tar as recovered in lay-product coking which residuum being an oily liquid still residue from the distillation and purification of the light oil comprises lower polymers and heavy monomers derived from the light oil and which is capable of acquiring by oxidation drying qualities and asphaltic characteristics in which mixture still residue preponderates by oxygen. dispersion through the mixture to a stage at which the mixture acquires by oxidation a melting-point substantially higher than normal room temperature while supplying to the mixture heat sumcient to maintain the mixture adequately liquid for the oxygen dispersion, resultantly to produce a homogeneous elastic and transparent filmforming mass in which the components are mutually compatible as an incident of their condition of admixture during oxidation.

7. As a material of commerce the film-forming composition herein described comprising in oxidized homogeneous admixture an oil having drying qualities and residuum derived from the arcmatic light oil which comprises the aromatics distilling below the boiling range of tar as recovered in by-product coking which residuum being an oily liquid still residue from the distillation and purification of the light oil comprises lower polymers and heavy monomers derived from the light oil.

8. As a material of commerce the film-forming composition herein described solid at temperatures at least as elevated as normal room temperature comprising in oxidized homogeneous admixture an oil having drying qualities and residuum derived from the aromatic light oil which comprises the aromatics distilling below the boiling range of tar as recovered in byproduct coking which residuum being an oily liquid still residue from the distillation and purification of the light oil comprises lower polymers and heavy monomers derived from the light oil.

9. As a material of commerce the film-forming composition herein described solid at temperatures substantially higher than normal room temperature comprising in oxidized homogeneous admixture an oil having drying qualities and residuum derived from the aromatic light oil which comprises the aromatics distilling below the boiling range of tar as recovered in by-product coking which residuum being an oily liquid still residue from the distillation and purification of the light oil comprises lower polymers and heavy monomers derived from the light oil, the said oxidized still residue preponderating in the composition.

FRANK W. CORKERY. 

